CN107778792A - Polymer blend - Google Patents

Polymer blend Download PDF

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Publication number
CN107778792A
CN107778792A CN201710744732.5A CN201710744732A CN107778792A CN 107778792 A CN107778792 A CN 107778792A CN 201710744732 A CN201710744732 A CN 201710744732A CN 107778792 A CN107778792 A CN 107778792A
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Prior art keywords
composition according
product
mass parts
laser
composition
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CN107778792B (en
Inventor
鲍里斯·诺伊瓦尔德
马蒂亚斯·比恩米勒
约阿希姆·莫里克
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Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/08—Polyesters modified with higher fatty oils or their acids, or with resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1629—Laser beams characterised by the way of heating the interface
    • B29C65/1635—Laser beams characterised by the way of heating the interface at least passing through one of the parts to be joined, i.e. laser transmission welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/003—PET, i.e. poylethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/006—PBT, i.e. polybutylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0026—Transparent
    • B29K2995/0027—Transparent for light outside the visible spectrum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C08K7/20—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Toxicology (AREA)
  • Electromagnetism (AREA)
  • Optics & Photonics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Epoxy Resins (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

The present invention relates to polymer blend.The present invention relates to the enhancing composition of the novel hydrolysis-stable based on polybutylene terephthalate, PET, styrene acrylonitrile copolymer and at least one aromatic epoxy compound, it is related to the purposes of its product for being used to produce laser-light transparent, and is related to its purposes in laser transmission welding.

Description

Polymer blend
Technical field
The present invention relates to based on polybutylene terephthalate, PET, styrene-acrylonitrile copolymerization The novel enhancing composition of thing and at least one aromatic epoxy compound, it is related to it and is used to produce hydrolysis-stable, laser The purposes of transparent product, and it is related to its purposes in laser transmission welding.
Background technology
The general principle of laser transmission welding is described in technical literature (Kunststoffe 87, (1997) 3,348-350； Kunststoffe 88,(1998),2,210-212；Kunststoffe 87(1997)11,1632-1640； Plastverarbeiter 50(1999)4,18-19；Plastverarbeiter 46 (1995) 9,42-46) in.
Laser transmission welding is heating and the attended operation almost simultaneous single stage process of wherein plastics.One company Highly transmissive coefficient must be had by connecing counter pair, and another has the high absorption coefficient in laser wavelength range.Welding Before process, there will be part to be welded to be placed on desired terminal position and apply connection pressure.
There is no appreciable heating, the transparent connection counter pair by bombardment with laser beams.Only in second connection pairing Laser beam is completely absorbed near surface layer in thing, and the laser thus can be converted into heat energy and melt plastics.Due to heat Conductive process, the transparent component also plastify in the region in connection area.Outside apply connection pressure and by plastic melt Expansion caused by internal connection pressure produce the bonding connections of these parts.The conventional laser used in laser transmission welding Source is high-performance diode laser (HDL, λ=900-1100nm) and solid-state laser (fibre laser), particularly Nd: YAG laser (λ=1060-1090nm), because almost all of technicolour and non-reinforced thermoplastic has High transmission coefficient in the wave-length coverage, this is the necessary prerequisite of transparent connection counter pair.Absorption connection pairing Thing, which has, is added to absorption pigment thereon, and it is typically the carbon black for producing the black for human eye these parts that these, which absorb pigment, Pigment.However, there is also the so-called infrared absorbent can in visible wavelength region with non-black color.Referring to：
(https://de.wikipedia.org/wiki/Laserdurchstrahlschwei%C3%9Fen).
The laser welding of semi-crystalline thermo is more difficult than amorphous products in principle, because laser beam passes through spherocrystal Scattering.This problem that all merocrystalline plastics run into is particularly evident in polybutylene terephthalate (PBT)：With with phase Polyamide 6 (PA6) sheet material of stack pile is compared, and PBT has much lower laser-light transparent degree, because because significant scattering is inclined It is higher herein to backscattering part.In addition, the light beam passed through is transmitted/disperseed to a greater extent.
Generally, and also in the context of the present invention, laser-light transparent degree (LT) by light measurer from 780 to Determined at wavelength in the range of 1100nm.The experimental provision used in the experiment of the present invention is as follows：Radiation source is radiation From visible ray to the Halogen lamp LED of the spectrum of near infrared ray.Radiated light is focused on by means of pinhole under light source.This is surveyed Test piece material is placed under radiation source at 70mm distance.These test sheet materials are that have 60 × 40 × 2mm3Size injection The test sheet material of molding.Sheet material is placed such that light beam incides center (cornerwise intersection point) place with 5mm radiuses On the sheet material/pass through the sheet material.Using two edge filters in the test sheet material downstream come by through spectrum wavelength Scope is reduced to 780 to 1100nm scope.The radiation intensity of filtered light is determined using photodiode detector.Empty light (beam path) is used as 100% reference on road.Only to be measured at a wavelength, but including currently used for In the spectral region of all optical maser wavelengths of laser transmission welding operation in the range of from 780 to 1100nm.
Insufficient laser-light transparent degree may cause the increased circulation time in laser welding operation, it is possible to create have scarce Sunken part, or may be even more so that can not possibly laser welding.To a certain extent, these shortcomings can be welded by increasing Time compensates.However, for longer welding duration, the possibility increase of burning or the decomposition of the material.
If average laser transparency is to be at a fairly low level, change may have particularly disadvantageous consequence, so as to So that welding operation may be carried out no longer in acceptable processing window.This also causes to damage.Because laser welding is typically Produce the final step of chain, in this defects of part represent the loss of all values that adds so far.
Therefore, for increasing polyester, the particularly PBT various approach of laser-light transparent degree (LT) be known.A kind of way Footpath is to be mixed low laser-light transparent degree PBT with high laser-light transparent degree mixes conjugate.For this purpose, EP 2 949 703 A1, JP2004/315805A1 and DE-A1-10330722 are disclosed using PET (PET) and are optionally in The other additive of phosphorus-containing compound or makrolon form.
The A1 of US 2005/165176 disclose SAN (SAN) be used for produce strengthen laser-light transparent Polybutylene terephthalate based articles purposes.
The composition that the A of JP 2,003 292752 teach PBT and/or PET, SAN and glass fibre is used to produce enhancing The purposes of the PBT based articles of laser-light transparent.
Finally, the composition comprising PBT, SAN and glass fibre is also by EP 0 392 357 Known to the A1 of A2, DE 19929302 and A1 of EP 1553138.
The shortcomings that these prior art solutions is when PET does not have the advantageous effect for laser-light transparent degree, separately Outer addition reduces the hydrolytic stability and/or mechanical property of laser-light transparent degree or the resulting product of infringement.
The content of the invention
By the present invention solves the problems, such as thus be increase the enhanced article based on PBT/PET blends laser-light transparent Degree, while keep hydrolytic stability or even improve hydrolytic stability without reducing mechanical property, particularly in flexural strength Or in terms of impact resistance.
The solution and subject of the present invention of the problem are to include A) polybutylene terephthalate, B) poly- terephthaldehyde Sour second diester, C) at least one SAN and D) at least one reinforcing agent composition and thus can give birth to The product of production.
The preferred solution and subject of the present invention of the problem are to include A) polybutylene terephthalate, B) it is poly- to benzene Dioctyl phthalate second diester, C) at least one SAN, D) at least one reinforcing agent and E) at least one aromatic series Epoxide, preferably have 2 end epoxy-functionals aromatic epoxy compound composition and thus can produce Product.
Unexpectedly, at least one SAN combined with least one hydrolysis stabilizer adds Add composition and the resulting product produced according to the present invention, these products show improved sharp compared with prior art Optical transparency is simultaneously still that hydrolysis-stable is, does not run into the infringement in mechanical property.
At least one SAN is added in PBT and PET blend allows the laser of enhanced article Welding, these products may be not subjected to laser welding so far due to the laser-light transparent degree of deficiency.This remains into other before causing The application of connection procedure can obtain.Alternately, the laser connection procedure exported with the laser reduced can be used, is thus increased Life-span added with laser to be used and thus improve the economy of laser transmission welding process.
Laser-transparent article is further characterized by hydrolytic stability and improved made of the composition according to the present invention Surface feel, this shows high gloss, tranquiler/more smooth surface and more preferable color perception.
Definition
In the context of the present invention, strengthen composition or product is characterized in that they include at least one filler or increasing Strong agent.
In the case of according to the producible product of the present invention, good mechanical property feature in the context of the present invention For the high level of izod (Izod) impact resistance, while maintain the high level of flexural modulus.Impact resistance describes structural material and existed The ability of apparatus with shock absorbing in the case of not broken.Hitting property of Izod impact test according to ISO 180 is to be used to determine material The standard method of the impact resistance of material.This include first by the arm of pendulum-type impact machine be maintained at specific height (=it is constant Potential energy) and most it discharges at last.The arm bumps against sample, makes its fracture.The energy that is absorbed by the sample determines impact energy. Impact resistance is calculated as the ratio (units of measurement of impact energy and sample in cross section：kJ/m2).In the context of the present invention, Impact resistance determines according to ISO 180-1U at 23 DEG C.
According to " http://de.wikipedia.org/wiki/Biegeversuch ", by the way that sample is positioned at into two On holder and at its center loading test hammer, flexural modulus is determined with 3 bend tests.In the situation of flat sample Under, flexural modulus is then calculated as below：
Wherein E=is with kN/mm2The flexural modulus of meter；lvThe distance between=holder in terms of mm；XH=in terms of kN The terminal that flexural modulus determines；XLThe initial point that=the flexural modulus in terms of kN determines；DL=the X in terms of mmHWith XLBetween it is curved It is bent；Sample Widths of the b=in terms of mm；Thickness of sample of the a=in terms of mm.In the context of the present invention, flexural modulus according to ISO178-A is determined at 23 DEG C.
Embodiment
The preferred embodiments of the present invention
Present invention is preferably related to the composition comprising the following and thus producible laser-transparent article
A) polybutylene terephthalate,
B) PET,
C) at least one SAN,
D) at least one reinforcing agent and
E) at least one aromatic epoxy compound.
Present invention is preferably related to the composition comprising the following and thus producible laser-transparent article
A) the polybutylene terephthalate of every 100 mass parts,
B) the PET of 0.5 to 34 mass parts,
C) at least one SAN of 0.5 to 34 mass parts, and
D) at least one reinforcing agent of 10 to 200 mass parts.
Present invention is preferably related to the composition comprising the following and thus producible laser-transparent article
A) the polybutylene terephthalate of every 100 mass parts,
B) the PET of 5 to 15 mass parts,
C) at least one SAN of 5 to 15 mass parts, and
D) at least one reinforcing agent of 20 to 100 mass parts.
Present invention is preferably related to the composition comprising the following and thus producible laser-transparent article
A) the polybutylene terephthalate of every 100 mass parts,
B) the PET of 0.5 to 34 mass parts,
C) at least one SAN of 0.5 to 34 mass parts,
D) at least one reinforcing agent of 10 to 200 mass parts, and
E) at least one aromatic epoxy compound of 0.01 to 30 mass parts.
Present invention is preferably related to the composition comprising the following and thus producible laser-transparent article
A) the polybutylene terephthalate of every 100 mass parts,
B) the PET of 5 to 15 mass parts,
C) at least one SAN of 5 to 15 mass parts,
D) at least one reinforcing agent of 20 to 100 mass parts, and
E) at least one aromatic epoxy compound of 2 to 15 mass parts.
In the form of the invention further relates to preferably combined with PET, the particularly preferred composition according to the present invention at least A kind of SAN and aromatic epoxy compound be used to producing hydrolysis-stable, enhancing, laser-light transparent The purposes of polybutylene terephthalate based articles.
The invention further relates to a kind of method for laser welding for being used to connect at least two parts, wherein at least one portion Part includes the composition according to the present invention.
The invention further relates to include A) PBT, B) PET, C) at least one SAN, D) at least A kind of reinforcing agent and E) composition of at least one aromatic epoxy compound is used to produce hydrolysis-stable, laser-light transparent system The purposes of product.
The invention further relates to a kind of by the way that at least one SAN to be added to provided use It is used to strengthen hydrolysis-stable, enhancing the PBT comprising at least one aromatic epoxy compound in the molding material of processing The method of base and PET based articles.
For clarity, it should be noted that the present invention cover hereinafter briefly referring to or in preferable scope It is interior it is specified in any desired combination be defined and parameter.The present invention relates to the composition according to the present invention, relate to And thus producible molding material, and further relating to by these molding producible systems including laser-welded article of material Product, wherein at least one part include the composition according to the present invention.Unless otherwise noted, otherwise cited standard should be understood that To mean in submission date effective version.
It is preferred that it is used to produce by injection molding or is used to further produce laser-light transparent in extrusion for blown-moulding The preparation of the composition according to the present invention of the molding material of product passes through at least one Mixing component, preferably batch mixer, spy Independent component is mixed in not preferred co-rotating twin screw extruder to carry out.This provides the molding material as intermediate product Material.These molding materials (also referred to as thermoplastic molding materials) can be only by component A), B), C), D) and E) form or remove Component A), B), C), D) and E) outside can also include other component, particularly A), B), C), D), E) and F).
Component A)
According to the present invention be used as component A) polybutylene terephthalate (PBT) [CAS numberings 24968-12-5] pass through Known method produces (Kunststoff-Handbuch [plastics hands by terephthalic acid (TPA) or its reactive derivatives and butanediol Volume], VIII volume, page 695 and thereafter, Karl Hanser Verlag [karr Han Zeer publishing houses], Munich 1973)。
As component A) PBT preferably comprise based on dicarboxylic acids at least 80mol%, preferably at least 90mol% to benzene two Formic acid group.
In one embodiment, component A be used as according to the present invention) have PBT to be used can be comprising not only to benzene two Formic acid group but also the group or tool that have from other aromatic dicarboxylic acids of 8 to 14 carbon atoms for having up to 20mol% There are the group of the aliphatic dicarboxylic acid from 4 to 12 carbon atoms, particularly phthalic acid, M-phthalic acid, naphthalene -2,6- diformazan Acid, 4,4 '-xenyl dioctyl phthalate, butanedioic acid, adipic acid, decanedioic acid, azelaic acid, cyclohexanediacetic, cyclohexane cyclohexanedimethanodibasic or The group of 2,5- furandicarboxylic acids.
In one embodiment, according to the present invention be used as component A) PBT, in addition to butanediol, can include be up to 20mol% other aliphatic diols with 3 to 12 carbon atoms or up to 20mol% with 6 to 21 carbon atoms Alicyclic diol, preferably propyl- 1,3- glycol, 2- ethyls propyl- 1,3- glycol, neopentyl glycol, amyl- 1,5- glycol, hex- 1,6- bis- The amyl- 2,4- glycol of alcohol, 1,4 cyclohexane dimethanol, 3- methyl, the amyl- 2,4- glycol of 2- methyl, the amyl- 1,3- bis- of 2,2,4- trimethyls The amyl- 1,5- glycol of alcohol, 2,2,4- trimethyls, 2- ethyl hex- 1,3- glycol, 2,2- diethyl propyl- 1,3- glycol, hex- 2,5- bis- Alcohol, 1,4- bis- (beta-hydroxy ethyoxyl) benzene, 2,2- double (4- hydroxy-cyclohexyls) propane, 2,4- dihydroxy -1,1,3,3- tetramethyls The group of double (the 3- beta-hydroxies ethoxyl phenenyl) propane of cyclobutane, 2,2- and double (the 4- hydroxy propyloxy groups phenyl) propane of 2,2-.
Be preferably used as component A) PBT have according to EN-ISO 1628/5 in each case at Ubbelohde (Ubbelohde) In phenol/o-dichlorohenzene (1 at 25 DEG C in viscosimeter:1 parts by weight) in measurement from 40 to 170cm3In/g range, especially It is preferred that from 50 to 150cm3In the range of/g, very particularly preferably from 65 to 135cm3Inherent viscosity in the range of/g.Root According to Mark-Houwink equations, inherent viscosity iV (also referred to as Staudinger (Staudinger) index or limiting viscosity) is with putting down Equal molecular mass is proportional, and is the extrapolation of the viscosity number VN in the case where polymer concentration disappears.Inherent viscosity can be by A series of measurements are estimated by using suitable approximation method (such as Billmeyer).VN [ml/g] is by capillary viscosity The measurement of meter, solution viscosity in such as Ubbelohde viscometer obtains.Solution viscosity is measuring for the mean molecule quantity of plastics.Molten It is measured on the polymer of solution using various solvents (m-cresol, tetrachloroethanes, phenol, 1,2- dichloro-benzenes etc.) and concentration. Viscosity number VN makes it possible to monitor processing and the performance characteristic of plastics.Can be with Study Polymer Melts through heated by means of comparing measurement Stress, ageing process or chemicals, weathering and the effect of light.In this respect, referring further to：http://de.wikipedia.org/ Wiki/Viskosimetrie and " http://de.wikipedia.org/wiki/Mark-Houwink-Gleichung”.
According to the present invention be used as component A) PBT can also be used in mixed way with other polymers.Used according to the invention The production of PBT blends is carried out by being kneaded.During this mixing action, it can be taken off in addition by conventional additives, particularly Mould agent or elastomer are added in melt to improve the characteristic of blend.
PBT used according to the invention can be from Cologne Lanxess Deutschland GmbH (Lanxess Deutschland GmbH) with titleWhat B 1300 was obtained.
Component B)
PET (PET) [CAS numberings 25038-59-9] is used as component B).Herein using various PET types, they are variant on existing catalyst for example in its viscosity and/or wherein.It can be equally total to using various PET Polymers, wherein with following monomer or the derivative modified PET of following monomer：Diethylene glycol, polyethylene glycol, hexamethylene diformazan Alcohol (cis-trans- or mixture), 2,2,4,4- tetramethyl -1,3- cyclobutanediols, norcamphane -2,3- dioctyl phthalate, isophthalic two Formic acid, tert-butyl isophthalic acid, the sodium of 5- sulfoisophthalic acids one, naphthalenedicarboxylic acid, hydroxybenzoic acid, adipic acid.
The ratio of such comonomer be generally the B based on 100 mass parts) be no more than 5 mass parts, preferably more than 2 mass parts.
Workable PET types can contain the catalyst for being generally used for its production.These include Ca, Mg, Zr, Mn, Zn, Pb, Sb, Sn, Ge and Ti salt, such as oxide, alkoxide and/or the salt as derived from organic acid, such as acetate, oxalates, lemon Complexing/complex compound of lemon hydrochlorate and/or lactate and also glycollate and these metals and its mixture.Root Residual metals content of these catalyst used according to the present invention in PET is preferably≤300ppm, particularly preferably≤260ppm.
The inherent viscosity that PET used according to the invention preferably has is from about 30 to 150cm3In the range of/g, especially It is preferred that from 40 to 130cm3In the range of/g, particularly preferably from 50 to 100cm3In the range of/g, it is in all cases According to ISO 1628 by Ubbelohde viscometer at 25 DEG C in phenol/o-dichlorobenzene (parts by weight 1:1) measurement in.
PET used according to the invention for example can protect Equipolymers with title LIGHTERTMC93 by the section of applying of Germany Company obtains.
Component C)
At least one SAN based on vinyl aromatic compounds (C.1) and acrylonitrile (C.2) It is used as component C) use.
Preferably as the copolymer C of 100 mass parts) when including the following
(C.1) vinyl aromatic compounds of 50 to 99 mass parts and/or cyclosubstituted vinyl aromatic compounds, And
(C.2) acrylonitrile of 1 to 50 mass parts.
Preferable compound (C.1) be styrene, α-methylstyrene, p-methylstyrene, p- chlorostyrene and/ Or methacrylic acid (C1-C8)-Arrcostab, particularly methyl methacrylate, EMA.
Preferable acrylonitrile is undersaturated nitrile, particularly acrylonitrile or methacrylonitrile, and/or (methyl) acrylic acid (C1-C8)-Arrcostab, particularly methyl methacrylate, n-butyl acrylate, tert-butyl acrylate, and/or unsaturated carboxylic acid Derivative.
The derivative of preferable unsaturated carboxylic acid is its acid anhydrides or acid imide, particularly maleic anhydride or n- phenyl Malaysia acyl Imines.
Particularly preferred monomer (C.1) is in these monomer styrenes, α-methylstyrene and methyl methacrylate At least one.
Preferable monomer (C.2) in these monomers acrylonitriles, maleic anhydride and methyl methacrylate at least one Kind.
Monomer very particularly preferably is (C.1) styrene and (C.2) acrylonitrile.Give especially preferred be known as SAN and the SAN with CAS numberings 9003-54-7, it is from Frankfort Styrolution Obtained by GmbH.
Component D)
It is preferred that using glass fibre to be used as component D).These preferably have out of 7 to 18 μ ms, more preferably from 9 Fibre diameter to 15 μ ms, and added in the form of continuous fiber or in the form of chopped or milled glass fibre.
According to " http://de.wikipedia.org/wiki/Faser-Kunststoff-Verbund ", a) have Chopped strand (also referred to as chopped fiber), the b of length in the range of from 0.1 to 1mm) with the length in the range of from 1 to 50mm The long fibre of degree, c) and there is length L>Made a distinction between 50mm continuous fiber.Fibre length can be for example by micro- Focal spot x-ray computer tomography (μ-CT) determination (including in the context of the present invention)；DGZfP can 2007- speeches 47。
It is preferred that with suitable sizing material system or adhesion promotor or adhesion promotor system to these fibre modifications, it is especially excellent Choosing is modified based on silane.
Silylation adhesion promotor very particularly preferably for pretreatment is the silane compound of logical formula (I)
(X-(CH2)q)k-Si-(O-CrH2r+1)4-k (I)
Substituent therein is defined as follows：
X：NH2-, HO-,
q：From 2 to 10, preferably from 3 to 4 integer,
r：From 1 to 5, preferably from 1 to 2 integer,
k：From 1 to 3 integer, preferably 1.
Especially preferred adhesion promotor is the silane compound from the following group：TSL 8330, amino Butyl trimethoxy silane, aminopropyltriethoxywerene werene, ammobutyltriethoxysilane and contain glycidyl Corresponding silane as substituent X.
In order to be modified to these glass fibres, the glass fibre for being used for surface coating based on 100 mass parts, preferably With in the range of 0.05 to 2 mass parts, particularly preferably in the range of 0.25 to 1.5 mass parts and especially from 0.5 to 1 Amount in the range of mass parts uses these silane compounds.
Because to provide the molding material or should be by the processing (mixing) of its producible product, these glass fibres exist There may be d97 the or d50 value lower than initially use glass fibre in the molding material or the product.Due to providing The processing of the molding material or end article, these glass fibres may have on the molding material or the end article Such as initially use shorter distribution of lengths.
Component E)
It is preferred that the hydrolysis stabilizer used is the epoxidised of epoxidised natural oil, epoxidised fatty acid ester or synthesis Compound.These compounds preferably have at least one terminal epoxy groups.
Preferable epoxidised natural oil is based at least one oil being selected from the group：Olive oil, linseed oil, coconut Oil, peanut oil, palm oil, castor oil, soybean oil or cod-liver oil.Give particularly preferably soybean oil.
The molecular weight of epoxidised natural oil is preferably in the range of from 500 to 1000g/mol.According to of the invention preferred The linseed oil or soybean oil used is wherein C18- carboxylic acid inclusion accounts for the mixture of leading triglycerides.
Epoxidised natural oil is generally produced by method familiar to the person skilled in the art；Referring to Angew.Chem. [applied chemistry world version] 2000,112,2292-2310.
Preferable epoxidised fatty acid ester is by the saturation with 10 to 40 carbon atoms, preferably 16 to 22 carbon atoms Or undersaturated aliphatic carboxylic acid by with the aliphatic saturated alcohols with 2 to 40 carbon atoms, preferably 2 to 6 carbon atoms What reaction obtained.
It is preferable when being related to list or dicarboxylic acids.Particularly preferably from lower group selection at least one carboxylic acid：N-nonanoic acid, palm fibre Palmitic acid acid, laurate, Heptadecanoic acide, dodecanedioic acid, behenic acid, stearic acid, capric acid, montanic acid, linoleic acid, leukotrienes and oil Acid.
Used preferable aliphatic saturated alcohols are monohydric alcohol and tetrahydroxylic alcohol.Particularly preferably when at least one alcohol selects From the following group when：N-butanol, n-octyl alcohol, stearyl alcohol, ethylene glycol, propane diols, neopentyl glycol, pentaerythrite and glycerine.Glycerine is outstanding Its is preferable.
The mixture of different esters and/or oil can also be used.
Epoxy-functional is introduced into above-mentioned ester and/or oil by it with epoxidizing agent, preferably with peracid, especially with mistake The reaction of acetic acid is carried out.Such reaction is that those skilled in the art are fully well known.
The production of the epoxidised compound of synthesis is equally well-known to those skilled in the art.The quilt preferably synthesized The compound of oxidation is：
- polyglycidyl ether or poly- (Beta-methyl glycidol) ether, by with least two free alcoholic extract hydroxyl groups or phenol The reaction of the compound of hydroxyl and/or by phenolic hydroxyl group and the epoxychloropropane that suitably substitutes preferably in the basic conditions or Obtained by reaction and subsequent basic treatment in the presence of acidic catalyst.
Preferable polyglycidyl ether or poly- (Beta-methyl glycidol) ether, derived from non-cyclic alcohol, particularly ethylene glycol, two Ethylene glycol and poly- (oxygen ethylidene) glycol of higher level, propane -1,2- glycol or poly- (oxygen propylidene) glycol, propane -1,3- Glycol, butane-Isosorbide-5-Nitrae-glycol, poly- (oxygen tetramethylene) glycol, pentane -1,5- glycol, hexane -1,6- glycol, hexane -2,4,6 Triol, glycerine, 1,1,1- trimethyl propane, double trimethylolpropane, pentaerythrite, D-sorbite, or derived from polycyclic oxygen chlorine Propane.
Alternately, preferable polyglycidyl ether or poly- (Beta-methyl glycidol) ether are derived from alicyclic alcohol, especially It is 1,3- or 1,4- dihydroxies butylcyclohexane, double (4- hydroxy-cyclohexyls) methane, double (4- hydroxy-cyclohexyls) propane of 2,2- or 1,1- Double (methylol) hexamethylene -3- alkene, or they include aromatic proton, such as N, double (2- ethoxys) aniline of N- or p, p '-bis- (2- hydroxyl second Base amino) diphenyl methane.
- epoxidised the compound preferably synthesized is the phenol based on monokaryon, phenol based on multinuclear or based in acid The phenol and the condensation product of formaldehyde obtained under the conditions of property.
Preferable mononuclear phenolic is resorcinol or hydroquinones.
Preferable polynuclear phenol is double (4- hydroxyphenyls) methane, double (4- hydroxyphenyls) propane of 2,2-, the double (3,5- bis- of 2,2- Bromo- 4- hydroxyphenyls) propane or 4,4 '-dihydroxy-diphenyl sulfone.
The preferable condensation product of phenol and formaldehyde is phenol novolacs.
Component E) the preferred aromatic epoxy compound that uses be the component with 2 end epoxy-functionals.
Aromatic epoxy compound is preferably the oligomeric reaction product with formula (II) of bisphenol-A and epoxychloropropane
Wherein n=0 to 10, preferably n=1 are to 8, particularly preferably n=1 to 6 and n corresponds in the reaction product The average of unit.
Aromatic epoxy compound used according to the invention preferably has in the range of from 0 DEG C to 150 DEG C, particularly preferably 50 DEG C to 120 DEG C, very particularly preferably in the range of from 60 DEG C to 110 DEG C and especially in the range of from 75 DEG C to 95 DEG C Softening point (Mei Tele companies (Mettler), DIN51920).
It is preferred that the aromatic epoxy compound used has in the range of from 160 to 2000g/eq, preferably 250 to 1200g/ Eq, the epoxy particularly preferably in the range of from 350 to 1000g/eq and particularly preferably in the range of from 450 to 800g/eq are worked as Measure weight (EEW；DIN16945).
Especially preferably use with titleFrom poly- (double obtained by Luo Yina Leuna Harze GmbH Phenol-A- copolymerization-epoxychloropropane) [CAS numberings 25068-38-6] be used as component E), about 600 to 1800g/mol MW.
Component F)
In one embodiment, according to the composition of the present invention except component A) to E) in addition to can also include and be different from group Point C), D) and E) and at least one additive F), and the group selected from the following：Phosphite ester stabilizer, releasing agent, UV are steady Determine agent, heat stabilizer, gamma-rays stabilizer, antistatic additive, flow promortor, fire retardant, elastomer modifier, flame-retardant additive, Emulsifying agent, nucleator, plasticizer, lubricant, dyestuff and pigment, with the proviso that this additive substantially reduce from 780 to Laser-light transparent degree in wave-length coverage in the range of 1200nm.
Preferably as the component A using every 100 mass parts) 0.1 to 100 mass parts, particularly preferred 0.3 to 20 quality The component F of part).Do not include when according to the molding material of the present invention except component A especially preferably) to F) in addition to it is other Composition.
As component F) additive preferably there is≤1000nm particle diameter, the result is that the additive is dissolved in really In PBT polymer substrate but do not cause the extra scattering of laser emission.On the contrary, insoluble in the polymer substrate and The component of refractive index with the refractive index for differing greatly from PBT can cause the scattering of laser emission.For example, these and in addition Suitable additive description existsM ü ller, Kunststoff-Additive [plastic additive], the 3rd edition, 3rd Edition, sweat Ze Er publishing house (Hanser-Verlag), Munich, Vienna, 1989 and in Plastics Additives Handbook [plastic additive handbook], the 5th edition, sweat Ze Er publishing houses, Munich, in 2001.As component F) additive Can also be individually or by mixture/use in the form of masterbatch.
Be used as component F when using at least one phosphite ester stabilizer) when be preferable.Following series is come from it is preferred that using At least one phosphite ester stabilizer：Three (2,4- di-tert-butyl-phenyls) phosphite esters (168, BASF AG (BASF SE), CAS numbering 31570-04-4), double (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites (626, Chemtura Corporation (Chemtura), CAS numbering 26741-53-7), double (2,6- di-t-butyl -4- methyl Phenyl) pentaerythritol diphosphites (ADK Stab PEP-36, Chinese mugwort Dicon A/S (Adeka), CAS numbering 80693-00-1), Double (2,4- dicumylphenyls) pentaerythritol diphosphites (S-9228, Dao Hua chemical company (Dover Chemical Corporation), CAS numbering 154862-43-8), three (nonyl phenyl) phosphite esters (TNPP, BASF AG, CAS numbering 26523-78-4), (2,4,6- tri-butyl-phenol) -2- butyl -2- ethyls -1,3-PD it is sub- Phosphate (641, Chemtura Corporation, CAS numbering 161717-32-4) orP-EPQ。
Preferably when being used as component F using at least one releasing agent) when.As preferable releasing agent, at least one choosing From the following group：One or more ester type waxes, pentaerythritol tetrastearate (PETS), long-chain fat acids, these long chain fatty acids One or more salt, one or more amide derivatives of these long chain fatty acids, lignite wax class and low point of one or more Sub- weight northylen or polypropylene wax or one or more Alathon waxes.
Preferable long chain fatty acids are stearic acid or behenic acid.The salt of preferable long chain fatty acids is calcium stearate or hard Resin acid zinc.The preferable amide derivatives of long chain fatty acids are ethylene bis stearamides.Preferable lignite wax class is with 28 To the mixture of straight chain, saturation the carboxylic acids of the chain length of 32 carbon atoms.
It is preferred that the heat or UV stabilizer that use are space Hinered phenols, hydroquinone type, aromatic amine class (such as diphenylamines Class), substitution resorcinol class, salicylic acid esters, benzotriazole and benzophenone, and also have these groups difference The representative thing or their mixture of ground substitution.
The plasticizer being preferably used is dioctyl phthalate, dibenzyl phthalate, O-phthalic acid butyl Benzyl ester, hydrocarbon oils or N- (normal-butyl) benzsulfamide.
According to the present invention, elastomer modifier is used as other F).It is grafted preferably with one or more Polymer.
Graft polymers as elastomer modifier is to be based on suitable graft base, preferably diene rubber, EP (D) M rubber, i.e. those based on ethylene/propene, and optional diene, acrylate, polyurethane, silicone, chlorobutadiene and Ethylene-vinyl acetate rubber.
Particularly preferred elastomer modifier is abs polymer (emulsion, body and suspending liquid A BS), is such as described in DE-A 2 035 390 or in DE-A 2 248 242, or Ullmann,der Technischen Chemie [Liv Ullmann industrial chemistry encyclopaedia], volume 19 (1980), page 280 and thereafter in.Gel in graft base Content is at least 30wt%, and preferably at least 40wt% (is measured) in toluene.ABS is understood to refer to acrylonitrile-butadiene-benzene EtheneCopolymer[CAS numberings 9003-56-9], and be to synthesize trimer by what following three kinds of different types of monomers were formed： Acrylonitrile, 1,3- butadiene and styrene.It is the thermoplastic of amorphous phase.Quantification can be from the third of 15%-35% The styrene change of alkene nitrile, 5%-30% butadiene and 40%-60%.
As component F) elastomer modifier/graft copolymer be by radical polymerization come caused by, such as pass through Emulsion, suspension, solution or polymerisation in bulk, preferably pass through emulsion or polymerisation in bulk.
Specially suitable graft rubber also includes abs polymer, and they are to use organic hydrogen according to US-A 4 937 285 The initiator system of peroxide and ascorbic acid is by Redox Initiator come caused by.
Method
Carry out being used to produce in injection mould by mixing independent component at least one Mixing component, preferably batch mixer The preparation of the composition according to the present invention of system or the molding material further used in extrusion.In order to produce laser-light transparent system Product, these molding materials are made to be subjected to being processed further, preferably be subjected to injection molding process or extrusion.The note of thermoplastic molding materials Mold system and extrusion method are known to persons of ordinary skill in the art.
The method of the invention of laser-transparent article is produced from 230 DEG C to 330 DEG C by extrusion or injection molding In the range of, under the melt temperature preferably from 250 DEG C to 300 DEG C, and optionally also under the pressure no more than 2500 bars, preferably Under the pressure no more than 2000 bars, particularly preferably under the pressure no more than 1500 bars and very particularly preferably no more than Carried out under 750 bars of pressure.
Preferably made a distinction in extrusion between section bar extrusion and order are coextruded.Order coextrusion is included by friendship The order the replaced material different to two kinds is in turn extruded.In this way, form in extrusion direction have it is different piecewise The preformed member of material composition.Possibly through appropriate material selection the spy definitely required is provided to multiple special article sections Property, for example, article is provided soft end and hard central section or integration soft corrugated regions (Thielen, Hartwig,Gust,“Blasformen von" [blown-moulding of hollow plastic body], card Er Hanzeer publishing houses (Carl Hanser Verlag), Munich 2006, the 127-129 pages).
Injection moulding is characterised by, (pellet shape is preferably in raw material in the circular cylindrical cavity that one has been heated Formula) melted (plasticizing), and injected under stress in a Temperature Control Type cavity as a kind of injection molding material. After the cooling (solidification) of material, injection moldings are stripped.
Distinguish following operate：
1. plasticizing/fusing
2. injection stage (padding)
3. kept for the pressure stage (due to the thermal contraction in crystallization process)
4. the demoulding.
Injection-molding machine includes closed cell, injecting unit, driver and control system.The closed cell includes fixing And it is movable for the platen of mould, end plate and multiple pull bars and the driver of the mold cramping platen movable for this (toggle link (toggle joint) or hydraulic pressure closure member).
Injecting unit includes can electrically heated bucket, the driver (motor, driver) for screw rod and for making this Screw rod and the hydraulic means of injection member movement.The injecting unit is used to melt, measure, inject and apply to keep pressure to exist In (due to the shrinking) powder/granulated materials.The problem of melt adverse current in the screw rod (aerial drainage), is able to by check-valves Solve.
In the injection mold, the melt entered is then separated and cooled down, and therefore produces to be produced Product.Need two half molds all the time to this.In injection molding, following functions system is distinguished：
- flow passage system
- shaping insert
- exhaust
- machine rack (mounting) and power absorb
- dismoulding system and motion transmission device
- temperature control
It is manufactured continuous herein using the molding material of the present invention in the extruder in extrusion compared with injection molding Plastic extrusion thing, the extruder be for produce shaping thermoplastic molded product machine.Distinguish the following：
Single screw extrusion machine and double screw extruder and corresponding subgroup, conventional single screw extrusion machine, the single spiral shell of conveying Bar extruder, counter rotating twin screW extruder and co-rotating twin screw extruder.
Extrusion device includes element extruder, mould, upstream device, extrusion-blown modling mould.For producing the extrusion of section bar Equipment includes elements below：Extruder, section bar mold, alignment unit, cooling zone, crawler type transfer device (take-off) and Roll-type transfer device, separator and inclination chute.
Finally, the present invention relates to by extrusion, section bar extrusion or injection molding acquisition and based on the group according to the present invention The transmission laser welding method of the product of compound.
Cited method produce unexpectedly have it is related for laser transmission welding process from 780 to The product with the mechanical property for keeping good of extraordinary laser-light transparent degree in 1200nm wave-length coverage, according to the present invention The product of laser-light transparent degree optimization can resist hydrolytic degradation by adding suitable hydrolysis stabilizer and exceptional stability in addition Change to increase without undesirable chain and process reduction that is stable or running into laser weldability in process with related.
In the context of the present invention, as described in more particularly in instances, by light measurer from 780 to Laser-light transparent degree (LT) is measured/determined in 1100nm whole wave-length coverage.
Article of the invention from the composition according to the present invention goes for transmission laser welding method.Preferably Article or the article as obtained by transmission laser welding method be for covering, the material of shell, sensor.Transmitted by laser Product obtained by welding obtain motor vehicles, electronics, telecommunications, information technology or computer industry and also have be in Application in front yard, motion, medicine and show business/be used in particular for these aspects.
Given according to the present invention and preferably include PBT, PET, SAN, one or more glass fibres and at least one The composition of aromatic epoxy compound and thus producible product.
Given according to the present invention and preferably include PBT, PET, SAN, one or more glass fibres and at least one The composition of aromatic epoxy compound with 2 end epoxy-functionals and thus producible product.
Given according to the present invention and preferably include PBT, PET, SAN, one or more glass fibres and at least one The composition of the aromatic epoxy compound of formula (II) with 2 end epoxy-functionals and thus producible product,
Wherein n=0 to 10, preferably n=1 are to 8, particularly preferably n=1 to 6, wherein n correspond in the reaction product Unit average.
Given according to the present invention and preferably include PBT, PET, SAN, one or more glass fibres and at least one The composition of aromatic epoxy compound with 2 end epoxy-functionals and thus producible product, the aromatic series Epoxide have in the range of from 0 DEG C to 150 DEG C, it is particularly preferred 50 DEG C to 120 DEG C, very particularly preferably from 60 DEG C to In the range of the 110 DEG C and especially softening point (Mei Tele companies, DIN 51920) in the range of from 75 DEG C to 95 DEG C.
Given according to the present invention and preferably include PBT, PET, SAN, one or more glass fibres and at least one The composition of aromatic epoxy compound with 2 end epoxy-functionals and thus producible product, the aromatic series Epoxide have from 160 to 2000g/eq, preferably 250 to 1200g/eq, particularly preferably from 350 to 1000g/ Epoxy equivalent weights (EEW, DIN16945) in the range of eq and particularly preferably in the range of from 450 to 800g/eq.
Given according to the present invention and preferably include PBT, PET, SAN, one or more glass fibres and at least one The composition of bisphenol A based epoxy resin and thus producible product.
Given preferably comprising PBT, PET, SAN, one or more glass fibres according to the present invention and at least had Poly- (bisphenol-A-copolymerization-epoxychloropropane) [the CAS numberings 25068-38-6's] of MW in the range of from 600 to 1800g/mol Composition and thus producible product.
Example
In order to produce composition having thus described the invention, the temperature in fusing in the range of from 285 DEG C to 310 DEG C In double screw extruder (from Stuttgart, Germany section times Long Wona and Fu Laideer limited companies under degree The Mega batch mixers of ZSK 26 of (Coperion Werner＆Pfleiderer)) in these single components are kneaded, extrusion, And cool down until that can be granulated and be pelletized.Before any further step, in vacuum drying chamber at 120 DEG C About 4h is dried to the granulated materials.
The sheet material for being used to assess and sample listed in table 1 be fusion temperature in the range of from 250 DEG C to 270 DEG C and Injection molding forms on commercially available injection-molding machine under mold temperature in the range of from 80 DEG C to 100 DEG C.
Laser-light transparent degree measures
The determination of laser-light transparent degree (LT) is carried out by light measurer in the whole wave-length coverage from 780 to 1100nm. Experimental provision is as follows：Radiation source is the Halogen lamp LED of spectrum of the radiation from visible ray near infrared ray.By means of pin under light source Hole aperture focuses on radiated light.The test sheet material is placed under radiation source at 70mm distance.These test sheet materials With 60 × 40 × 2mm3Size injection-molded test sheet material.Sheet material is placed such that light beam is incided with 5mm On the sheet material at center (cornerwise intersection point) place of radius/pass through the sheet material.Use two streamlines in the test sheet material downstream Formula filter is reduced to 780 to 1100nm scope come the wave-length coverage for the spectrum that will travel across.Use photodiode detector The radiation intensity of the filtered light of measure.Empty light path (beam path) is used as 100% reference.The example reported in table 1 and In comparison example, " o " represents sufficient laser-light transparent degree, wherein can realize that up to the economic of 1.5mm thickest swashs Photocoagulation method.In the comparison, "-" represents low 25% transparency and " -- " 50% transparency that represented low.In table 1 "+" represent with regard to laser-light transparent degree measurement for for " o " be higher than 25% value.
Flexural modulus and flexural strength
The flexural modulus (Pa unit) and flexural strength of the product produced by the thermoplastic molding materials of the present invention are roots Determined according to ISO 178-A at 23 DEG C in crooked test.Alternative selection for measure passes through EN ISO 527 (http://de.wikipedia.org/wiki/EN_ISO_527-1) provide.The flexural strength of mark " o " should manage in table 1 Solve to mean to reduce compared with the example for marking "+" 10% flexural strength.
Impact resistance
In with 80 × 100 × 4mm3Size sample form by the present invention thermoplastic molding materials produce The impact resistance of product determines (kJ/m at 23 DEG C according to ISO 180-1U in shock-testing2Unit).
Impact resistance after hydrolysis
To be in that there is 80 × 100 × 4mm3Size sample form by according to the present invention composition production system Product in the Constant Climate cabinet KMF240 of Tuttlingen, Germany Bin De companies (Binder) (come from) 85 DEG C and 85% it is relative Stored 1000 hours under humidity.Then the anti-of stored product is determined at 23 DEG C in shock-testing according to ISO 180-1U Impact (kJ/m2Unit).In the example and comparison example reported in table 1, "+" represent compared with the sample not stored Impact resistance after storage less than 30% is reduced.In the comparison, compared with the sample not stored accordingly, "-" represents to reduce 50% impact strength and " -- " represent to reduce the impact strength more than 60%.
Reactant
PBT：With 94g/cm3Inherent viscosity polybutylene terephthalate (B1300, from the bright Sheng in Cologne Germany Co., Ltd is commercially available)
PET：With 80g/cm3Inherent viscosity PET (LIGHTERTMC93, German Shi Kebao Equipolymers companies)
SAN：SAN (SAN M 60, the Ineos benzene neck in Frankfurt, Germany city are public Take charge of (Ineos Styrolution))
Glass fibre (GF)：Glass fibre (the CS of diameter glued using the compound of silane-containing and that there are 10 μm 7967, the commercially available product from Antwerp, BEL Lanxess Corporation (Lanxess N.V., Antwerp, Belgium))
Hydrolysis stabilizer：The oligomeric reaction product of bisphenol-A and epoxychloropropane (referring to formula (I)), 500 to 700g/eq's Epoxy equivalent weights (DIN 16945) and softening point (Mei Tele companies, DIN 51920) [CAS between 75 DEG C and 90 DEG C Numbering 25068-38-6]
Other additive：Especially may be used for the amount of PBT of all examples based on 100 mass parts 1.0 mass parts Commercially available phosphite ester stabilizer and/or releasing agent：From Mu Dunzi Clariant International Ltd. of Switzerland (Clariant International Ltd.)E。
From table 1 it is clear that with based on be based only upon as the PBT (contrast 1) of sole polymer component or based on only PBT and The product of the polymer composition of PET mixture (contrast 2) is compared, the product (example 1 and 2) of the composition based on the present invention Show with the notable preferably laser transmission value for keeping good mechanical property.In addition, after weather storage, according to this hair Bright composition (example 2) shows the hydrolytic resistance for keeping good and the transmission of significantly improved laser.
Table 1
The amount for the component reported in table 1 is to be represented in all cases with parts by weight.

Claims (15)

1. the composition comprising the following and thus producible product
A) polybutylene terephthalate,
B) PET,
C) at least one SAN, and
D) at least one reinforcing agent.
2. composition according to claim 1 and thus producible product, it is characterised in that based on A) 100 mass The polybutylene terephthalate of part, the composition and product include
B) the PET of 0.5 to 34 mass parts,
C) at least one SAN of 0.5 to 34 mass parts,
And
D) at least one reinforcing agent of 10 to 200 mass parts.
3. composition according to any one of claim 1 and 2 and thus producible product, it is characterised in that institute State composition and additionally comprise E) at least one hydrolysis stabilizer.
4. composition according to claim 3 and thus producible product, it is characterised in that based on A) 100 mass The polybutylene terephthalate of part, the composition include at least one hydrolysis stabilizer of 0.01 to 30 mass parts.
5. composition according to any one of claim 1 to 4 and thus producible product, it is characterised in that make Component D is used as by the use of glass fibre).
6. composition according to any one of claim 1 to 5 and thus producible product, it is characterised in that make Group is used as by the use of at least one SAN based on vinyl aromatic compounds (C.1) and acrylonitrile (C.2) Divide C).
7. composition according to claim 6 and thus producible product, it is characterised in that 100 mass parts are total to Polymers C) include
(C.1) vinyl aromatic compounds of 50 to 99 mass parts and/or cyclosubstituted vinyl aromatic compounds, and
(C.2) acrylonitrile of 1 to 50 mass parts.
8. composition according to claim 7 and thus producible product, it is characterised in that using styrene, α- Methyl styrene, p-methylstyrene, p- chlorostyrene, and/or methacrylic acid (C1-C8)-Arrcostab is as (C.1).
9. composition according to claim 7, it is characterised in that use acrylonitrile or methacrylonitrile and/or (methyl) Acrylic acid (C1-C8The derivative of)-Arrcostab and/or unsaturated carboxylic acid is as (C.2).
10. composition according to any one of claim 1 to 9 and thus producible product, it is characterised in that (C.1) selected from least one of monomer styrene, α-methylstyrene and methyl methacrylate.
11. composition according to any one of claim 1 to 9 and thus producible product, it is characterised in that (C.2) selected from least one of monomers acrylonitrile, maleic anhydride and methyl methacrylate.
12. composition according to any one of claim 1 to 9 and thus producible product, it is characterised in that make As (C.1) and acrylonitrile is used as (C.2) by the use of styrene.
13. composition according to any one of claim 3 to 12 and thus producible product, it is characterised in that Component E is used as using epoxidised natural oil, epoxidised fatty acid ester or the epoxidised compound of synthesis) hydrolysis-stable Agent.
14. the composition according to any one of claim 1 to 13 is used to produce enhancing, laser-light transparent gather to benzene two The purposes of formic acid fourth diester based articles.
15. method for laser welding, it is characterised in that at least one part to be welded includes appoints according in claim 1 to 13 Composition described in one.
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